Not applicable.
Not applicable. REFERENCE TO A MICROFICHE APPENDIX
Not applicable.
This invention is directed to a water based fiber treatment agent and method for treating fibers. In particular, the water based fiber treatment agent can impart to fibers either perfect smoothness, lubricating properties, reduced tackiness, or pleasant tactile sensation. The invention is also directed to methods of treating fibers to impart to the fibers perfect smoothness, lubricating properties, reduced tackiness, or pleasant tactile sensation.
Water based fiber treatment agents composed of silicone oil emulsions are disclosed in Japanese Laid Open Patent Applications [Kokai] Sho 55-34228 and Hei 4-198321. Furthermore, [Kokai] Sho 64-45466/U.S. Pat. No. 4,891,398 (Jan. 2, 1990) and [Kokai] Hei 3-152275/U.S. Pat. No. 5,232,611 (Aug. 3, 1993) each disclose water based fiber treatment agents in which such an emulsion is combined with a polyorganosilsesquioxane powder.
However, these water based fiber treatment agents either cannot impart to fibers sufficient smoothness, lubricating, and adhesion prevention properties, or they have low stability.
It is therefore an object of the invention to provide water based fiber treatment agents which impart to fibers a perfect smoothness, lubricating properties, reduced tackiness, or pleasant tactile sensation. Another object is to provide methods of treating fibers to impart to the fibers perfect smoothness, lubricating properties, reduced tackiness, or pleasant tactile sensation.
These and other features of the invention will become apparent from a consideration of the detailed description.
Not applicable.
The water based fiber treatment agent of this invention is characterized by being made from a silicone oil emulsion of crosslinked silicone particles with an average diameter of 0.01 to 100 xcexcm which are in silicone oil drops with an average diameter of 0.05 to 500 xcexcm, which are in turn dispersed in water. The diameter of the crosslinked silicone particles is smaller than the diameter of the silicone oil drops.
The method of the invention for treating fibers is characterized in that the fibers are treated with a water based fiber treatment agent made of a silicone oil emulsion of crosslinked silicone particles with an average diameter of 0.01 to 100 xcexcm in silicone oil drops having an average diameter of 0.05 to 500 xcexcm, which are dispersed in water. Again, the diameter of the crosslinked silicone particles is smaller than the diameter of the silicone oil drops.
Following is a more detailed description of the silicone oil emulsion of the present invention. Thus, the treatment agent of the invention is characterized by comprising a silicone oil emulsion that contains crosslinked silicone particles in silicone oil drops which are then dispersed in water. The crosslinked silicone particles contained in the emulsion are obtained by crosslinking a crosslinkable silicone composition.
This composition can be prepared by causing a hydrosilation crosslinking reaction, a condensation crosslinking reaction, an organic peroxide type crosslinking reaction, or a high energy ray crosslinking reaction. The most preferable reactions are hydrosilation crosslinking reactions or condensation crosslinking reactions.
There are no special limitations relative to the type of silicone oil used for forming the silicone oil drops, but the silicone oil preferably should have a completely linear, partially branched linear, cyclic, or branched chain molecular structure. The most preferable structure is a linear molecular structure. It is preferred that a silicone oil be used which does not participate in the crosslinking reaction during formation of the crosslinked silicone particles.
Thus, the silicone oil should not participate in the reaction or be obstructive to the reaction. For example, where the crosslinked silicone particles are formed by a hydrosilation crosslinking reaction, the silicone oil should be a silicone oil which does not contain in its molecules any alkenyl groups and silicon bonded hydrogen atoms. In this regard, the silicone oil can be a dimethylpolysiloxane having both molecular terminals capped with trimethylsiloxy groups, a methylphenylpolysiloxane having both molecular terminals capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups, a copolymer of methyl-(3,3,3-trifluoropropyl)-siloxane and dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups, a cyclic dimethylpolysiloxane, or a cyclic methylphenylsiloxane.
Among these silicone oils, part of the hydrogen atoms in any hydrocarbon group in a side chains and on a molecular terminal can be substituted by polyether groups, carboxyl groups, or epoxy groups. When the crosslinked silicone particles are formed by means of a condensation crosslinking reaction, the silicone oil can be a compound which does not contain in its molecule silanol groups, silicon bonded hydrogen atoms, or silicon bonded hydrolyzable groups. Representative silicone oils are dimethylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, methylphenylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, copolymers of methylphenylsiloxane and dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups, copolymers of methyl-(3,3,3-trifluoropropyl)-siloxane and dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups, cyclic dimethylpolysiloxanes, cyclic methylphenylsiloxanes, dimethylpolysiloxanes having both molecular terminals capped with dimethylvinylsiloxy groups, copolymers of methylvinylsiloxane and dimethylsiloxane having both molecular terminals capped with dimethylvinylsiloxy groups, methylvinylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, or cyclic methylvinylsiloxanes. Again, some of the hydrogen atoms in hydrocarbon groups on the molecular terminals and in the side chains of these types of silicone oils can be substituted by amino groups, amide groups, epoxy groups, carboxyl groups, or polyether groups.
Although there are no special limitations with regard to the viscosity of these silicone oils, it is preferred that the viscosity be within the range of 1 to 100,000,000 mPaxc2x7s at 25xc2x0 C., most preferably 5 to 10,000,000 mPaxc2x7s, at 25xc2x0 C.
It is, however, necessary that the average diameter of silicone oil drops in the emulsion be within a range of 0.05 to 500 xcexcm, and preferably within a range of 0.05 to 200 xcexcm. This is for the reason that an average diameter of silicone oil drops below the lower limit or above the upper limit of this range causes the water based fiber treatment agent to lose its stability.
It is also necessary that the average diameter of crosslinked silicone particles in the emulsion be within a range of 0.01 to 100 xcexcm, and preferably within a range of 0.05 to 50 xcexcm. This is for the reason that emulsions with an average diameter of crosslinked silicone particles below the lower limit or above the upper limit of this range possess low stability.
In addition, and as should be apparent, in emulsions of this invention the diameter of the crosslinked silicone particles should be smaller than the diameter of the silicone oil drops.
The crosslinked silicone particles may have a spherical, thread like, flat, or an irregular shape. A spherical shape is preferred. Furthermore, irrespective of the characteristics of the crosslinked silicone particles, the emulsion can be obtained in a gel like, rubber like, or similar elastomeric form.
Silicone oil emulsions of the invention can be prepared by a number of different methods. According to a first method, crosslinked silicone particles are preliminarily uniformly dispersed in a silicone oil, and then mixture is emulsified in water.
According to a second method, a silicone oil emulsion can be obtained by preliminarily emulsifying a silicone oil in water which is then mixed with a crosslinked silicone particle suspension obtained by preliminarily emulsifying crosslinked silicone particles in water.
However, in the first method, the crosslinked silicone particles cannot be uniformly dispersed in the silicone oil, so it is difficult to prepare a silicone oil emulsion that would contain crosslinked silicone particles in silicone oil drops dispersed in water.
On the other hand, in the second method, the crosslinked silicone particles and silicone oil drops are dispersed independently, it is difficult to prepare a specific silicone oil emulsion which would contain crosslinked silicone particles in silicone oil drops dispersed in water.
For these reasons, it is most preferred to prepare the silicone oil emulsion by dispersing in water, a crosslinkable silicone composition which contains a non-crosslinkable silicone oil, and then conducting the crosslinking reaction. It should be understood that the non-crosslinkable silicone oil should be used in an amount that exceeds the amount of non-crosslinkable silicone oil that can be held in the crosslinked product obtained from the crosslinkable silicone composition.
The crosslinkable silicone composition can be of a type that produces as a result of crosslinking, a crosslinked product in the form of a gel, rubber, or similar elastomer. For example, it can be the result of a hydrosilation crosslinking type reaction, a condensation crosslinking type reaction, an organic peroxide crosslinking type reaction, or a high energy ray crosslinking type reaction. The most preferable types of reactions are hydrosilation crosslinking reactions and condensation crosslinking reactions.
The hydrosilation crosslinking reaction silicone composition comprises at least an organopolysiloxane having in its molecule at least two alkenyl groups, an organopolysiloxane having in its molecule at least two silicon bonded hydrogen atoms, and a catalyst for the hydrosilation reaction.
Alkenyl groups in the first mentioned organopolysiloxane can be represented by vinyl groups, allyl groups, butenyl groups, pentenyl groups, and hexenyl groups. Most preferred are vinyl groups. This organopolysiloxane can also contain monovalent hydrocarbon groups other than alkenyl groups bonded to silicon atoms such as methyl groups, ethyl groups, propyl groups, butyl groups, or other similar alkyl groups; cyclopentyl groups, cyclohexyl groups, or other similar cycloalkyl groups; phenyl groups, tolyl groups, xylyl groups, or other similar aryl group; benzyl groups, phenethyl groups, 3-phenylpropyl groups, or other similar aralkyl groups; and 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, or other similar halogenated hydrocarbon groups. This organopolysiloxane groups may have a linear, cyclic, network like, or partially branched linear molecular structure. In order to form elastomer like crosslinked silicone particles such as gel or rubber like particles, linear and partially branched linear structures are most preferred. While there are no special limitations with regard to the viscosity of the first mentioned organopolysiloxane, it should have a viscosity that does not limit dispersing of the crosslinkable silicone composition in water. Therefore, it is preferable that the viscosity be within a range of 20 to 100,000 mPaxc2x7s, preferably between 20 and 10,000 mPaxc2x7s at 25xc2x0 C.
The examples of silicon bonded groups other than silicon bonded hydrogen atoms present in the second mentioned organopolysiloxane are the same as the monovalent hydrocarbon groups noted above in the first mentioned organopolysiloxane. The second mentioned organopolysiloxane may have a linear, cyclic, network like, or partially branched linear molecular structure. Again, although there are no special limitations with regard to the viscosity of the second mentioned organopolysiloxane, it should be one that does not limit dispersing the crosslinkable silicone composition in water. Preferably, its viscosity should be within a range of 1 to 10,000 mPaxc2x7s at 25xc2x0 C.
It is preferred that the second mentioned organopolysiloxane be used in the crosslinkable silicone composition in an amount sufficient for curing the composition, but preferably in an amount of 0.3 to 200 parts by weight based upon 100 parts by weight of the first mentioned organopolysiloxane.
The hydrosilation reaction catalyst contained in the crosslinkable silicone composition is any catalyst for accelerating crosslinking. A platinum catalyst is preferred. Some examples of platinum catalyst are chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, platinum black, or a platinum catalyst on a silica carrier.
In manufacturing products using the method of the present invention, a crosslinkable silicone composition that contains a hydrosilation catalyst in water can be prepared by (i) dispersing in water, a crosslinkable silicone composition which has been premixed with an hydrosilation catalyst, or (ii) a crosslinkable silicone composition can be dispersed in water without the catalyst, and then the catalyst can be added to water. In either case, it is preferred that the aqueous dispersion contain a hydrosilation catalyst with an average particle diameter not exceeding 1 xcexcm.
The hydrosilation catalyst should be present as a component of the crosslinkable composition in an amount sufficient for accelerating the crosslinking of the crosslinkable composition. For example, in the case of platinum based systems, the catalyst should be used in an amount to provide 1xc3x9710xe2x88x927 to 1xc3x9710xe2x88x923 parts by weight of platinum metal based upon 100 parts by weight of the composition.
The condensation crosslinking reaction type silicone composition comprises an organopolysiloxane which contains a hydrolyzable group such as an aminoxy group, an acetoxy group, an oxime group, an alkoxy group, or hydroxyl group, bonded to at least two silicon atoms in its molecule; a silane type crosslinking agent having a hydrolyzable group such as an aminoxy group, an acetoxy group, an oxime group, or an alkoxy group, bonded to at least three silicon atoms in its molecule; and a condensation reaction catalyst such as an organic titanium compound or an organic tin compound.
In this organopolysiloxane, the alkoxy groups can be represented by methoxy groups, ethoxy groups, and methoxyethoxy groups; and the oxime groups can be represented by dimethylketoxime groups and methylethylketoxime groups. Other groups can be bonded to silicon atoms in the organopolysiloxane such as monovalent hydrocarbon groups represented by methyl groups, ethyl groups, propyl groups, butyl groups, or similar type alkyl groups; cyclopentyl groups, cyclohexyl groups, or similar type cycloalkyl groups; vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups; phenyl groups, tolyl groups, xylyl groups, or similar type aryl groups; benzyl groups, phenethyl groups, 3-phenylpropyl groups, or similar type aralkyl groups; 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, or similar halogenated hydrocarbon type groups. This organopolysiloxane may have a linear, cyclic, network like, or partially branched linear molecular structure. Linear or partially branched linear molecular structures are preferred for forming gel like and rubber like elastomer type crosslinked silicone particles.
Although there are no special limitations with regard to the viscosity of the organopolysiloxane, it should not limit the dispersing of the crosslinkable silicone composition in water. Therefore, it is preferably a viscosity within the range of 20 to 100,000 mPaxc2x7s, preferably between 20 and 10,000 mPaxc2x7s at 25xc2x0 C.
The oxime groups and the alkoxy groups in the silane type crosslinking agent can be the same as those noted above. The silane type crosslinking agent can be represented by methyltrimethoxysilane, vinyltrimethoxysilane, methyltrioximosilane, and vinyltrioximosilane. It is preferred that the silane type crosslinking agent be used in an amount sufficient for curing the crosslinkable silicone composition, and preferably that it be present in an amount of 0.3 to 200 parts by weight based upon 100 parts by weight of the organopolysiloxane composition.
Condensation reaction catalysts such as organic tin compounds and organic titanium compounds are intended for accelerating the crosslinking reaction of the crosslinkable silicone compound. Such catalysts can be represented by dibutyltin dilaurate, dibutyltin diacetate, tin octoate, dibutyltin dioctoate, tin laurate, tetrabutyl titanate, tetrapropyl titanate, and dibutoxy bis(ethylacetoacetate) titanate.
The condensation reaction catalyst should be used in an amount sufficient to crosslink the crosslinkable silicone composition, and preferably in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based respectively upon 100 parts by weight of the organopolysiloxane composition.
If desired, a filler can be added to the crosslinkable silicone composition for adjusting its flowability or for improving the mechanical strength of the resulting crosslinked silicone particles. Some examples of suitable fillers are precipitated silica, fumed silica, baked silica, fumed titanium oxide, or similar reinforcing filler; crushed quartz, diatomaceous earth, aluminosilicic acid, ferrous oxide, zinc oxide, calcium carbonate, or similar nonreinforcing filler. The surfaces of these types of fillers can be treated with hexamethyldisilazane, trimethylchlorosilane, a polydimethylsiloxane, a polymethylhydridosiloxane, or a similar organosilicon compound.
The non-crosslinkable silicone oil that is contained in the crosslinkable silicone composition should be one which does not make any contribution to the reaction of crosslinking of the composition itself. Although there are no special limitations with regard to viscosity, the viscosity should be one which will ensure the dispersion in water of the crosslinkable silicone composition containing the non-crosslinkable silicone oil. Preferably therefore, the non-crosslinkable silicone oil should have a viscosity of 1 to 100,000,000 mPaxc2x7s, preferably between 2 and 10,000,000 mPaxc2x7s, at 25xc2x0 C. In addition, the non-crosslinkable silicone oil may be an organopolysiloxane having a linear, partially branched linear, cyclic, or branched molecular structure. Linear and cyclic molecular structures are the most preferred.
When the crosslinkable silicone composition is an hydrosilation crosslinking reaction type, it is preferred that the non-crosslinkable silicone oil contain no alkenyl groups or silicon bonded hydrogen atoms in its molecule. Some suitable examples of such oils are dimethylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, methylphenylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, copolymers of methylphenylsiloxane and dimethylsiloxane having trimethylsiloxy groups on both molecular terminals, copolymers of methyl-(3,3,3-trifluoropropyl) siloxane and dimethylsiloxane having trimethylsiloxy groups on both molecular terminals, cyclic dimethylpolysiloxanes, and cyclic methylphenylsiloxanes. A portion of the side chains and/or the hydrogen atoms in terminal hydrocarbon groups in these molecules can be substituted with epoxy groups, carboxy groups, or polyether groups.
For the crosslinkable silicone which is a condensation crosslinking reaction type, it is preferred that the non-crosslinkable silicone oil not contain silanol groups, silicon bonded hydrogen atoms, or silicon bonded hydrolyzable groups in its molecule. Examples of appropriate silicone oils are dimethylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, methylphenylpolysiloxanes having both of molecular terminals capped with trimethylsiloxy groups, copolymers of methylphenylsiloxane and dimethylsiloxane having trimethylsiloxy groups on both molecular terminals, copolymers of methyl-(3,3,3-trifluoropropyl)-siloxane and dimethylsiloxane having trimethylsiloxy groups on both molecular terminals, cyclic dimethylpolysiloxanes, cyclic methylphenylsiloxanes, dimethylpolysiloxanes having both molecular terminals capped with dimethylvinylsiloxy groups, copolymers of methylvinylsiloxane and dimethylsiloxane having both molecular terminals capped with dimethylvinylsiloxy groups, methylvinylpolysiloxanes having both molecular terminals capped with trimethylsiloxy groups, and cyclic methylvinylsiloxanes. Part of the side chains or the hydrogen atoms in any terminal hydrocarbon groups in these molecules of silicone oil can, if desired, be substituted by amino groups, amide groups, epoxy groups, carboxy groups, and polyether groups.
The non-crosslinkable silicone oil contained in the crosslinkable compound should be used in an amount sufficient for maintaining the non-crosslinkable silicone oil in the product of the crosslinking of the crosslinkable silicone composition. In particular, it should be used in excess of the quantity of the non-crosslinkable oil that can be held by the product of the crosslinking. The amount that can be held is different for each combination of crosslinkable silicone composition and non-crosslinkable silicone oil. In general, however, the non-crosslinkable silicone oil should be used in an amount within the range of 200 to 5,000 parts by weight, preferably 250 to 2,000 parts by weight, based upon 100 parts by weight of crosslinkable silicone composition.
The method for preparing emulsions according to the may consist of dispersing a crosslinkable silicone composition that contains the non-crosslinkable silicone oil in water, and then conducting the crosslinking reaction. Dispersing the crosslinkable silicone composition in water can be carried out using a homomixer, a paddle mixer, an Henschel mixer, a homodisperser, a colloid mixer, a propeller type stirrer, an homogenizer, an inline type continuous emulsifier, an ultrasound emulsifier, or a vacuum kneader.
Water should be used in an amount of 5 to 99 weight percent, preferably 10 to 80 weight percent based upon the total weight of the emulsion. To improve stability of the crosslinkable silicone composition in water, and to ensure dispersion, the composition may be combined with a nonionic surface active agent, a cationic surface active agent, or an anionic surface active agent. Nonionic surface active agents are preferred. The surface active agent should be used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based upon 100 parts by weight of the crosslinkable silicone composition containing the non-crosslinkable silicone oil.
The emulsion of the crosslinkable silicone composition is then either heated, maintained at room temperature, or irradiated with high energy rays, whereby the crosslinking reaction is caused to occur in the crosslinkable silicone composition dispersed in water.
Treatment agents according to this invention may contain other components such as liquid paraffin, magnesium stearate, calcium stearate, or similar organic oils and lubricants. In addition, there can be included antistatic agents, charge suppressing agents, bactericidal agents, preservative agents, and anticorrosive agents.
These treatment agents can be used as oils for application to raw yarn, raw cotton, stuffing, wool blends, nylon staple fibers, acrylic staple fibers, and in knitting, spinning, as well as for application to sewing threads or spandex urethane elastic yarns, to impart smoothness and lubricity. They can also be used for rayon, regenerated fibers, acetate fibers, semiregenerated fibers, polyester fibers, or other synthetic fiber.
When the silicone oil contains epoxy or carboxyl groups, the treatment agent can be used as a napping agent for raised fabrics; a hand improver for enhancing softness, smoothness, compression recovery, antiwrinkling properties, and stretch recovery; a finishing agent for deep coloring and heavy dyeing of polyester fabrics; an antimelting finishing agent for sportswear; or as a tack improver in a waterproofing agent to impart water repellency. When the silicone oil contains polyether groups and is used as a treating agent, a stable treatment agent can be obtained even when another surfactant is not added.
The method for treating fibers according to the invention is characterized in that fibers are treated with a water based fiber treatment agent. Treatments using water based fiber treatment agents can be carried out in a number of ways, one example of which is a method in which the water based fiber treatment agent is diluted with water or used without being diluted, and applied to a cloth, yarn, cotton, or tow, by spraying, by a kiss roll, or by gravure printing, and then dried or heat treated.
Generally, the water based fiber treatment agent should be applied to the fiber such that the combined amount of the crosslinked silicone particles and the silicone oil, i.e., the add-on solids in the water based fiber treatment agent, be between 0.01 and 8 weight percent. In the case of polyester, nylon, or other raw yarn or raw cotton, the amount should be between 0.2 and 1.0 weight percent. When the object of the treatment is to improve hand of a textile fabric made from cotton or blends of polyester and cotton, the amount should be between 0.3 and 1.0 weight percent. For sewing thread or spandex yarn in particular, the amount should be between 3 and 10 weight percent.